Supramolecular Complexation-Enhanced CO2 Chemisorption in Amine-Derived Sorbents.

A supramolecular complexation approach is developed to improve the CO2 chemisorption performance of solvent-lean amine sorbents. Operando spectroscopy techniques reveal the formation of carbamic acid in the presence of a crown ether. The reaction pathway is confirmed by theoretical simulation, in which the crown ether acts as a proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO2 capacity and diminished energy consumption in sorbent regeneration are achieved.

Development of Controllable Hetero-Pauson-Khand Polymerization to Functional Stimuli-Responsive Poly(γ-lactam)s.

Polymers containing lactam structures play a crucial role in both natural biological systems and human life, and their synthesis, functions and applications are of utmost importance for biomimetics and the creation of new materials. In this study, we developed an efficient heterogeneous Pauson-Khand polymerization (h-PKP) method for the controlled synthesis of main-chain poly(γ-lactam)s containing α, ß-unsaturated γ-lactam functionalities using readily available internal alkynes and imines. The molecular weights of the resulting poly(N-Ts/γ-lactam)s can be precisely controlled by adjusting the ratio of phenyl formate and nickel. These polymers exhibit high solid-state luminescence and demonstrate rapid and sensitive dual responsiveness to light and acid stimuli. They further demonstrate strong reactive oxygen species (ROS) generation capability. The unique dual-emission peaks observed in poly(N-H/γ-lactam)s obtained through post-treatment under acidic conditions demonstrate a mechanism of aggregation-induced intermolecular excited-state proton transfer specific to lactam structures. The efficient one-pot synthetic method for poly(γ-lactam) provides a novel strategy for constructing polymers with γ-lactam structures in the main chain and the simple and efficient post-modification method offer a versatile toolbox for functionalizing poly(γ-lactam)s to expand their potential applications.

Intramolecular carbolithiation cascades as a route to a highly strained carbocyclic framework: competition between 5-exo-trig ring closure and proton transfer.

The preparation of fairly strained carbocyclic ring systems by intramolecular 5-exo-trig ring closure has been well documented, and the absence of proton transfers that would compromise such cyclizations is a hallmark of this chemistry. In an effort to explore the limitations of this approach to more highly strained systems, the preparation of a stellane (tricyclo[3.3.0.0(3,7)]octane) framework by an intramolecular carbolithiation cascade involving three coupled 5-exo-trig cyclizations of the vinyllithium derived from 2-bromo-4-vinyl-1,6-heptadiene by lithium-bromine exchange was investigated. The cascade does not afford the stellane; rather, the cascade is terminated after two cyclizations by a proton transfer that occurs by an intermolecular process catalyzed by trace amounts of endo-5-methyl-2-methylenebicyclo[2.2.1]heptane present in reaction mixtures as a consequence of inadvertent quenching of an intermediate alkyllithium during prolonged reaction times at room temperature.

Exploring the influence of intermolecular hydrogen bonding on the fluorescence properties of HQCT and HQPH fluorescent chemosensors.

Recently, two trace water detection probes, 8-hydroxyquinoline-2-carboxaldehyde thiosemicarbazone(HQCT) and 8-hydroxyquinoline-2-carboxaldehyde (pyridine-2-carbonyl)-hydrazine(HQPH) have been successfully designed in the experiment. The original intramolecular proton transfer can be prevented by the water molecules, leading to fluorescence quenching. In order to investigate the fluorescence quenching mechanism, the effect of water molecules on the excited state proton transfer process will be studied in detail. In this contribution, the six models have been optimized and the related analysis have been carried out. When water molecules are involved in the proton transfer process, the energy barrier decreases significantly and the conversion of the enol structure to the keto structure is accelerated. Moreover, the intermolecular hydrogen bonding, not participating in the proton transfer process, can facilitate the proton transfer process by affecting the distribution of the electrostatic potential within the molecule, which in turn lowers the energy barrier for proton transfer.

Quadruple Anticounterfeiting Encryption: Anion-Modulated Forward and Reverse Excitation-Dependent Multicolor Afterglow in Two-Component Ionic Crystals.

Molecule-based afterglow materials with ultralong-lived excited states have attracted great attention owing to their unique applications in light-emitting devices, information storage, and anticounterfeiting. Herein, a series of new types of two-component ionic crystalline materials were fabricated by the self-assembly of cytosine and different anions under ambient conditions. The multiple intermolecular interactions of cytosine with phosphate and halogens anions can lead to abundant energy levels and different crystal stacking modes to control molecular aggregation and excited-state intermolecular proton transfer (ESIPT) process. Interestingly, H-aggregation-induced green to yellow room-temperature phosphorescence (RTP) and ESIPT-dominated cyan RTP to deep blue thermally activated delayed fluorescence (TADF) emission can be generated by tuning excitation wavelength, time evolution, and temperature. Furthermore, the combination of two-component ionic crystals can be used as multicolored candidates for quadruple information encryption. Therefore, this work not only develops an anion-modulated strategy to achieve color-tunable afterglow from both static and dynamic fashions but also provides a guideline for designing forward/reverse excitation-dependent luminescent materials.

Efficient Colorimetric Fluoride Anion Sensor Based on π-Conjugated Carbazole Small Molecule.

The ability to detect fluoride anions with high selectivity and sensitivity by using the naked eye is crucial yet challenging. In this study, a novel, simple conjugated organic dye, N-tert-butyldimethylsilyl-3,6-diiodocarbazole (CA-TBMDS) was developed and used for the first time as a colorimetric sensor for fluoride. CA-TBMDS was found to be a highly sensitive fluoride chemosensor, with a detection limit as low as 3 × 10-5 M. The reaction of CA-TBMDS with fluoride anions in a tetrahydrofuran solution resulted in a color change from colorless to yellow under ambient light, which can be discriminated by the naked eye. The sensor operated via intermolecular proton transfer between the amide units and the fluoride anion, as confirmed by proton nuclear magnetic resonance titration. CA-TBMDS is not only highly sensitive to fluoride anions, but also exhibits high sensitivity in the presence of various ions. This work demonstrates that N-butyldimethylchlorosilane-based organic dyes have prospective utility as a type of fluoride anion chemosensor.

The investigation of excited state proton transfer mechanism in water-bridged 7-azaindole.

Based on the time-dependent density functional theory (TDDFT), the excited-state intermolecular proton transfer (ESIPT) mechanism of water-bridged 7-azaindole has been investigated theoretically. The calculations of primary bond lengths and the IR vibrational spectra between the S0 state and the S1 state that verified the intramolecular hydrogen bond were strengthened. The fact that reproduced experimental absorbance and fluorescence emission spectra well theoretically demonstrate that the TDDFT theory we adopted is reasonable and effective. In addition, intramolecular charge transfer based on the frontier molecular orbitals demonstrated the indication of the ESIPT reaction. The constructed potential energy curves of ground state and the first excited state based on keeping the H2···O3 and H6···N7 distances fixed at a series of values have been used to illustrate the ESIPT process. A relative lower barrier of 5.94 kcal/mol in the S1 state potential energy curve for type II (lower than that of 9.82 kcal/mol in the S1 state for type I) demonstrates that type II ESIPT process occurs firstly in 7Al-2H2O complex.

Ground-State Intermolecular Proton Transfer of N2O4 and H2O: An Important Source of Atmospheric Hydroxyl Radical?

To evaluate the significance of the generation of atmospheric hydroxyl radical from reaction of N2O4 with H2O, CASPT2//CASSCF as well as CASPT2//CASSCF/Amber QM/MM approaches were employed to map the minimum-energy profiles of sequential reactions, NO2 dimerization and ground-state intermolecular proton transfer of trans-ONONO2 as well as the photolysis of HONO. A highly efficient ground-state intermolecular proton transfer of trans-ONONO2 is found to dominate the generation of hydroxyl radical under atmospheric conditions. Although proton transfer occurs with high efficiency, the precursor reaction of dimerization producing trans-ONONO2 has to overcome a 17.1 kcal/mol barrier and cannot compete with the barrierless channel of symmetric O2N-NO2 formation from isolated NO2 monomers. Our computations reveal that the photolysis of HONO without a barrier definitely makes significant contributions to the concentration of the atmospheric hydroxyl radical, but its importance is influenced by the lack of trans-ONONO2 isomer in the atmospheric environment.